The effects of Ni and Li doping on the performance of lithium manganese oxide material for lithium secondary batteries

Layered Li_0.7[M_1/6Mn_5/6]O₂ (M=Li, Ni) was synthesized using a sol-gel method. P2-Na_0.7[M_1/6Mn_5/6]O₂ precursor was first synthesized by a sol-gel method, and then O2-Li_0.7[M_1/6Mn_5/6]O₂ was prepared by an ion exchange of Li for Na in P2-Na_0.7[M_1/6Mn_5/6]O₂ precursor. From charge/discharge curves, it was seen that Li_0.7[Li_1/6Mn_5/6]O₂ has two plateaus similar to those observed from a spinel structure, but Li_0.7[Ni_1/6Mn_5/6]O₂ holds a single plateau as observed from a typical layered structure. It was considered that Li_0.7[Li_1/6Mn_5/6]O₂ undergoes a phase transformation from layered to spinel structure during the charge/discharge cycle, but Li_0.7[Ni_1/6Mn_5/6]O₂ maintains O2-layered structure after the cycles. Li_0.7[Ni_1/6Mn_5/6]O₂ was higher in discharge capacity and retention rate than Li_0.7[Li_1/6Mn_5/6]O₂.     

A porous mixed-valent iron MOF exhibiting the acs net: Synthesis, characterization and sorption behavior of Fe3O(F4BDC)3(H2O)3·(DMF)3.5

A new mixed-valent iron MOF, formulated as Fe₃O(F₄BDC)₃(H₂O)₃·(DMF)_3.5 (1), has been synthesized by using a perfluorinated linear dicarboxylate to link trigonal prismatic Fe₃(μ³-O)(O₂C–)₆ clusters. The structure refinement based on single crystal X-ray diffraction data collected from 1 reveals the material exhibits the acs topology with large channels along the crystallographic c-axis. Due to the presence of fluorine atoms the organic link, 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate (F₄BDC), has a 63° torsion angle between the carboxylate and aromatic planes, resulting in larger channels compared to those in the isoreticular material MOF-235. While few iron-based MOFs have demonstrated porosity, nitrogen and hydrogen sorption experiments carried out at 77 K proved the porosity of outgassed 1, which has a Langmuir surface are of 635 m²/g and a gravimetric capacity of 0.9 wt% of hydrogen at 1 bar.     

Thermal conductivity of high polymers—the influence of molecular weight

Some earlier observations on the influence of molecular weight, plasticizer, and irradiation on the thermal conductivity of polymers is reviewed. Also some new data on polystyrene and some new calculations based on the theory of Hansen and Ho are presented. These data show almost a two fold increase in the thermal conductivity of polystyrene as the molecular weight goes from 900 to 100,000. Data on the moleculer weight effect on thermal conductivity appear to be consistent with the theoretical calculations.     

Characterization of poly(vinylidenefluoride-co-hexafluoropropylene)-based polymer electrolyte filled with TiO2 nanoparticles

Nanoscale TiO₂ particle filled poly(vinylidenefluoride-co-hexafluoropropylene) film is characterized by investigating some properties such as surface morphology, thermal and crystalline properties, swelling behavior after absorbing electrolyte solution, chemical and electrochemical stabilities, ionic conductivity, and compatibility with lithium electrode. Decent self-supporting polymer electrolyte film can be obtained at the range of <50 wt% TiO₂. Different optimal TiO₂ contents showing maximum liquid uptake may exist by adopting other electrolyte solution. Room temperature ionic conductivity of the polymer electrolyte placed surely on the region of >10⁻³ S/cm, and thus the film is very applicable to rechargeable lithium batteries. An emphasis is also be paid on that much lower interfacial resistance between the polymer electrolyte and lithium metal electrode can be obtained by the solid-solvent role of nanoscale TiO₂ filler.     

Synthesis and kinetic studies of UV‐curable urethane‐acrylates

The UV‐curable urethane‐acrylates based on 2‐hydroxyethyl methacrylate (HEMA)‐terminated polyurethane (PU) for lithographic and coating applications are investigated in this study. Series of PU prepolymers were made from 4,4‐diphenyl methane diisocyanate (MDI), poly(propylene oxide) glycol (PPG 400), poly(butylene adipate)glycol (PBA 500), or poly(tetramethylene oxide) glycol (PTMO 1000) and are terminated with HEMA. The 2,2‐azobisisobutyronitrile (AIBN) was used as a UV‐initiator under air atmosphere. The curing kinetics of HEMA‐terminated PU film were studied. The curing analysis, using FTIR and reaction kinetics, indicate the reaction rate equation correlates well with the film thickness [T], initiator concentration [I], unreacted double bond concentration [C?C], and exposed energy [E] of the reaction system. The kinetic rate equation for the UV‐curable reaction can be written as © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3162–3166, 2004     

Lipase-catalyzed alcoholysis of triglycerides for short-chain monoglyceride production

Lipase from Pseudomonas fluorescens efficiently catalyzed the alcoholysis of various TG in dry alcohols. For TG with short-chain FA, more MG were accumulated. The yields of MG were affected by the alcohols used. The maximum yields of MG were as follows: 85% for monoacetin in n-butanol, 96% for monobutyrin in ethanol or n-butanol, 50% for monocaprylin in n-butanol, 48% for monolaurin in isopropanol, and 45% for monopalmitin in isopropanol. The MG produced were judged to be 2-MG by TLC analysis. The presence of organic cosolvent affected the reaction rate of the lipase-catalyzed alcoholysis of TG. For the alcoholysis of various TG in ethanol and cosolvent (1∶1, vol/vol), the rates had the following orders: (i) for tributyrin, hexane > toluene > acetone > ethyl acetate > chloroform > acetonitrile > pyridine; (ii) for tricaprylin, hexane > acetone > toluene > acetonitrile > ethyl acetate > pyridine > chloroform; and (iii) for trialurin, hexane > acetonitrile=acetone > ethyl acetate > pyridine=chloroform > toluene.     

Creep and Stress Rupture Behavior of an Advanced Silicon Nitride: Part I, Experimental Observations

Cylindrical buttuohead specimens of an advanced silicon nitride were tested in uniaxial tension at temperatures between 1422 and 1673 K. In the range 1477 to 1673 K, creep deformation was reliably measured using high-temperature contact probe extensometry. Extensive scanning and transmission electron microscopy has revealed the formation of lenticular cavities at two-grain junctions at all temperatures (1422–1673 K) and extensive triple-junction cavitation occurring at the higher temperatures (1644–1673 K). Cavitation is believed to be part of the net creep process. The stress rupture data show stratification of the Monkman–Grant lines with respect to temperature. Failure strain increased with increase in rupture time or temperature, or decrease in stress. Fractography showed that final failure occurred by subcritical crack growth in all specimens.     

Characteristics of polyvinylpyrrolidone-layered silicate nanocomposites prepared by attrition ball milling

Polyvinylpyrrolidone (PVP)/sodium montmorillonite (MMT) nanocomposites prepared via the solution intercalation method were investigated by UV/vis, SEM, X-ray diffraction, TEM, FT-IR and PLM (polarized light microscopy). PVP/MMT nanocomposites show exfoliation below 20 wt% MMT and intercalation above this concentration. Nanocomposites retain good optical clarity and increased thermal resistance with MMT content. The compatibility between PVP and MMT and their enhanced properties may be explained by hydrogen bonding interactions. In addition, the nanocomposites prepared under more rigorous mixing conditions show better transparency because the smaller particle sizes are induced. In addition, the study on optically clear PVP/MMT suspensions helps one to understand how optical anisotropy of MMT is affected by the existence of polymer in aqueous solution.     

Effect of reaction kinetics of polymer electrolyte on the ion‐conductive behavior for poly(oligo oxyethylene methacrylate)–LiTFSI mixtures

The effect of the reaction kinetics on the ionic conductivity for a comblike‐type polyether (MEO) electrolyte with lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) was characterized by DSC, complex impedance measurements, and ¹H pulse NMR spectroscopy. The ionic conductivity of these electrolytes was affected by the reaction condition of the methacrylate monomer and revealed by the glass transition temperature (T_g), spin–spin relaxation time (T₂), steric effects of the terminal groups, and the number of charge carriers indicated by the VTF kinetic parameter. In this system, the electrolytes prepared by the reaction heating rate of 10°C/min of MEO–H and 15°C/min of MEO–CH₃ showed maximum ionic conductivity, σ_i, two to three times higher in magnitude than that of the σ_i of the others at room temperature. As experimental results, the reaction kinetic rate affected the degree of conversion, the ionic conductivity, and the relaxation behaviors of polyether electrolytes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2149–2156, 2003     

Effect of low molecular weight polybutadiene as processing aid on properties of silica‐filled styrene–butadiene rubber compounds

Because silica has strong filler–filler interactions, a silica‐filled rubber compound shows a poor filler dispersion compared to a carbon black‐filled one. Improvement of the filler dispersion in silica‐filled styrene–butadiene rubber (SBR) compounds was studied using low molecular weight polybutadiene (liquid PBD) with the high content of 1,2‐unit. By adding the liquid PBD to the silica‐filled SBR compound, the filler dispersion and flow property are improved. The cure time and cure rate become faster as the 1,2‐unit content of the liquid PBD increases for the compounds containing the liquid PBD. The crosslink density increases linearly with increase in the 1,2‐unit content of the liquid PBD. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3135–3140, 2003